Electrochemistry cyclic voltammogram

Figure 5. Cyclic voltammograms of (a) 2,5"" -di-methyl-a-hexathiophene and (b) poly(2,2 -bithio-phene) films in acetonitrile containing 0.1 M E NCIO 103 (Reprinted from G. Zotti, G. Schia-von, A. Berlin, and G. Pagani, Electrochemistry of end-ca )ed oligothienyls-new insights into the polymerization mechanism and the charge storage, conduction and capacitive properties of polythiophene, Synth. Met. 61 (1-2) 81-87, 1993, with kind permission from Elsevier Science S.A.)...

If the film is nonconductive, the ion must diffuse to the electrode surface before it can be oxidized or reduced, or electrons must diffuse (hop) through the film by self-exchange, as in regular ionomer-modified electrodes.9 Cyclic voltammograms have the characteristic shape for diffusion control, and peak currents are proportional to the square root of the scan speed, as seen for species in solution. This is illustrated in Fig. 21 (A) for [Fe(CN)6]3 /4 in polypyrrole with a pyridinium substituent at the 1-position.243 This N-substituted polypyrrole does not become conductive until potentials significantly above the formal potential of the [Fe(CN)6]3"/4 couple. In contrast, a similar polymer with a pyridinium substituent at the 3-position is conductive at this potential. The polymer can therefore mediate electron transport to and from the immobilized ions, and their voltammetry becomes characteristic of thin-layer electrochemistry [Fig. 21(B)], with sharp symmetrical peaks that increase linearly with increasing scan speed. 

The situation is the contrary for the electrochemical behavior of the two cycles. These show distinct cyclic voltammograms due to the altered spatial distribution of the three electroactive CpFe groups. The differences in the electrochemistry of 83 and 84 are not dramatic but significant and their interpretation is not straightforward. A cycle with smaller bridging units such as 85, forcing the... 

Cyclic voltammetry is perhaps the most important and widely used technique within the field of analytical electrochemistry. With a theoretical standard hydrogen electrode at hand, one of the first interesting and challenging applications may be to try to use it to make theoretical cyclic voltammograms (CVs). In following, we set out to do this by attempting to calculate the CV for hydrogen adsorption on two different facets of platinum the (111) and the (100) facets. 

Re(bpy)(CO)3Cl-modified electrodes has not yet been explained. However, from the cyclic voltammograms of fac-Re(bpy)(CO)3Cl (Fig. 14) and from the intermediate complexes formed by electrolysis in acetonitrile in the presence and absence of C02, two different electrocatalytic pathways (Fig. 15) were suggested144 initial one-electron reduction of the catalyst at ca. -1.5 V versus SCE followed by the reduction of C02 to give CO and C03, and initial two-electron reduction of the catalyst at ca. -1.8 V to give CO with no C03. The electrochemistry of [Re(CO)3(dmbpy)Cl] (dmbpy = 4,4 -dimethyl-2,2 -bipyridine) was investigated145 to obtain mechanistic information on C02 reduction, and the catalytic reac-... 

FIGURE 3.6 Determination of the reduction potential of rubredoxin by electrochemistry and by EPR monitored bulk titration. The (+) data are from cyclic voltammograms taken at different temperatures the ( ) point is from low temperature EPR monitored titrations at ambient temperature or at 80°C. (Data from Hagedoorn et al. 1998.)... 

In 1986, Breikss and Abruna reported electrochemical and mechanistic studies on a close analogue of the rhenium complex, (Dmbpy)Re[CO]3Cl, where Dmbpy = 4,4 dimethyl 2,2 bipyridine. The cyclic voltammogram of the complex at platinum in CH3CN/tetrabutylammonium perchlorate is shown in Figure 3.56 for simplicity we will consider only the electrochemistry taking place above c. —2.3V vs. SCE. 

In addition, all complexes display a reversible, one-electron reduction at a very negative potential Em —1.70 to -1.90 V vs Fc+/Fc, which is metal centered and nearly invariant with respect to the substitution pattern of the coordinated pheno-lates. It demonstrates the enormous stabilization of the high-spin ferric state by three phenolato ligands. The electrochemistry also nicely shows that unprotected ortho- or para positions of these phenolates lead to irreversible electron-transfer waves on the time scale of a cyclic voltammogram and that methyl substituents are inefficient protecting groups. 

Electrochemistry. The cyclic voltammogram of Compound 87a was measured and is compared to octa. S -benzyl porphyrazine, Ni[pz(A4)] A = difS -benzyl), 60a (from Section IV.B.l) in Table XXIV. Compound 87a has two reversible ring reductions, which are more positive than those measured for H2 pc and more negative than those measured for Ni[pz(.V-benzyl)8], 60a, suggesting that the conformational influences of the peripheral seven-membered ring make this pz harder to reduce than the pz with unconstrained peripheral thioethers. Because these compounds are of limited solubility and cannot be oxidized or reduced readily, they appear to be unsuitable for use as building blocks for molecular conductors. 

Electrochemistry. The cyclic voltammograms of porphyrazines 215,217, 219, and 220 are given in Table XXXII. Compound 215, which has six dimethylamino substituents is much easier to oxidize than a typical porphyrazine, including Compounds 217,219, and 220. In fact, the oxidation potential is very close to those reported for M[pz(A-Me2)8] (101), which is still the most easily oxidized pz known to date. 

The electrochemistry of dioxoosmium(VI) complexes has also been extensively studied. The tra 5-dioxoosmium(VI) complexes of polypyridyl and macrocyclic tertiary amine ligands display very similar proton-coupled electron transfer couples. In aqueous solutions at pH < 5-7 the cyclic voltammograms of n-a i-[0s (0)2(bpy)2] show a remarkable reversible three-electron couple and a one-electron Os coimle. In the Pourbaix diagram two break points are observed in the pH dependence of the Os couple, which correspond to the pAa values of Os —OH2 and Os —(OHXOH2) (Figure 10). The redox reactions are shown in Equations (41)-(43). At pH >8 the 3e Os wave splits into a pH-independent le Os wave and a 2e/2H" Os wave (Equations (44) and (45)). 

Fig. 26 Reductive electrochemistry data for (70). (a) Solid line cyclic voltammogram after one-electron reduction dashed line cyclic voltammogram after 2.2 electron reduction.

This is mainly due to their laborious purification procedures and their required chemical modification for solubilization. Only recently, Prato et al. reported the electrochemistry of carbon nanotubes functionalized using the 1,3-dipolar cycloaddition reaction.120 The cyclic voltammogram obtained is shown in Fig. 8.9. 

The cyclic voltammograms of these soluble assemblies show a behavior similar to that previously observed by Prato et al.121, that is, a continuum of cathodic current with the reduction onset voltage of —0.15 V versus SCE. Recently, Paolucci et al. were able to obtain the electrochemistry of reduced unfunctionalized carbon nanotubes that were solubilized by reduction with alkali metals to their respective polyelectrolyte salts.122... 

These salts were found to be soluble in polar organic solvents as well as in water. Their electrochemistry also shows a continuum of current due to the successive filling of electronic states of the nanotube. Figure 8.11 shows the cyclic voltammogram obtained for nanotubes reduced using sodium metal. Close observation reveals two broad waves around —0.81 and 1.01 V, which have been attributed to the more complex electronic structure of the pristine materials, as compared to derivatized nanotubes. This observation is in agreement with recent calculations indicating... 

Fig. 10.3. General electrochemical performance of MPA-Gly-Gly-His modified electrodes for the detection of Cu2+ ions. Cu2+ ions are complexed to Gly-Gly-His in the accumulation process and are electrochemically reduced to Cu(0) to give UPD Cu. (a) Cyclic voltammograms of MPA-Gly-Gly-His modified electrodes in 50 mM ammonium acetate (pH 7.0) and 50 mM NaCl at 25°C at a scan rate of lOOrnVs-1 (i) before accumulation of metal ions and (ii) after accumulation in 46 nM Cu2+ in 50 mM ammonium acetate (pH 7.0) for 10 min. Multiple cycles in the copper voltammogram illustrate stable electrochemistry, (b) Cathodic Osteryoung square wave voltammograms of MPA-Gly-Gly-His modified gold electrodes in 50 mM ammonium acetate (pH 7.0) and 50 mM NaCl (i) before accumulation of metal ions and (ii) after accumulation in 46 nM Cu2+ in 50 mM ammonium acetate (pH 7.0) for 10 min. Reprinted from Ref. [12]. Copyright (2005) with permission from Elsevier.

It is of interest to examine quantitatively such potential-dependent redox equilibria as determined by SERS in comparison with that obtained by conventional electrochemistry. Figure 1 shows such data determined for Ru(NH3 )6 3" 2+at chloride-coated silver. The solid curves denote the surface concentrations of the Ru(III) and Ru(II) forms as a function of electrode potential, normalized to values at -100 and -500 mV vs SCE. These are determined by integrating cyclic voltammograms for this system obtained under conditions [very dilute (50 yM) Ru(NH3)63 +, rapid (50 V sec-1) sweep rate] so that the faradaic current arises entirely from initially adsorbed, rather than from diffusing, reactant (cf. ref. 6b). The dashed curves denote the corresponding potential-dependent normalized Ru(III) and Ru(II) surface concentrations, obtained from the integrated intensities of the 500 cm 1 and 460 cm-1 SERS bands associated with the symmetric Ru(III)-NH3 and Ru(II)-NH3 vibrational modes.(5a)... 

The azo function [e.g., azobenzene (PhN=NPh)] is reduced in a manner that is similar to that for quinones (discussed above). The electrochemistry for azo groups is a part of the discussion of the nitrogen compounds in Chapter 11 (Figure 11.10 illustrates the cyclic voltammogram for azobenzene). 

Figure 13.8 illustrates the reductive electrochemistry for (TPP)Con in CH2C12, DMF, and THF, and provides clear evidence that (TPP)Co reacts with CH2C12. Electrogenerated (porT)Af reacts with C02, which is illustrated by the cyclic voltammograms for (TPP)Con, carbon dioxide, and their combination in DMF (Figure 13.9). The reduction of carbon dioxide is an irrevers-...

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